Water-insoluble azodyestuffs



Patented Mar. 3, 1936 UNITED STATES No Drawing, Application October 22, 1932, Serial No. 639,153. In Germany October 26, 1931 7 Claims. (01. 260-461) The presentinvention relates to new waterlnsoluble azodyestufis, more particularly it relates to dyestuffs which may be represented by the probable general formula:

wherein X stands for NH, the hydrogen atom of which may be substituted by a hydrocarbon radical, S, SO, S02, 0, CH2 or CO, wherein R stands for a radical of the aromatic series, the N02- group stands in o-position to the azo group and wherein the nuclei may be further substituted by substituents which do not cause solubility in water, such as alkyl, alkoxy, aryloxy, aralkyloxy, halogen, the nitro group, acylamino, a sulfoneamide group one or both hydrogen atoms of which are substituted by hydrocarbon radicals, sulfonealkyl, sulfonearalkyl, sulfonearyl, an alkyl ketone or aryl ketone group; as substituents there a may be mentioned by way of example methyl,

ethyl, propyl, isobutyl, methoxy, amyLbenzyl, methoxybenzyl, chlorobenzyl, phenyl chlorophenyl, tolyl, anisyl, ethoxy, phenoxy, p-chlorophenoxy, benzyloxy, p-nitrobenzyloxy, chlorine, bromine, acetylamino, benzoylamino, monoor dimethylsulfoneamide, methyl-ethyl-sulfoneamide, phenylsulfoneamide, ethylphenylsulfoneamide, benzylsulfoneamide and the methylketone or ethylketone group. i

I As diazotization components suitable for the manufacture of the new dyestufis there may be mentioned amino-diphenylene compounds, such as 2-amin03-nitrodiphenyleneoxide, 3-amino-2- nitrodiphenylene'oxide, l-aminu-Z-nitrodiphenyleneoxide, 2-amino-3 nitro-G-bromodiphenyleneoxide, 2 -.amino 3,7-dinitrodiphenyleneoxide, 2- amino 3-nitro-6-sulfodiethylamidodiphenyleneoxide, 2-amin0-3-nitro-6-ethylsulfoneoxide, 2- amino 3- nitro-7-methoxydiphenyleneoxide, 1- methyl 2 amino 3 nitrodiphenyleneoxide, 3- amino 2 nitrocarbazole, 3 amino 4 nitrocarbazole, 2 amino 3 nitrocarbazole, 1-amino 2 nitrocarbazole, 3-amino-2-nitro-6- chloro'carbazole, 2-amino-3-nitro-7-sulfodimethy'laminocarbazole, 3 amino-2-nitro-6-methoxycarbazole', 3 amino2.6fdinitrocarbazole, 35amrio 2 nit'ro 7 m ethylketonecarbazole, 3- amino-2- nitro-9-methylcarbaaole, 3-ar'ni-nof l-nitro-9 -ethylcarbazole, 2 amino-3-nitro9-benzylcarbazole, 9-phenyl-3-amino-2-nitro 6 chlorocarbazole, 2- amino 3-nitro 7-bromofluorenone, 2-amino-3fldinitrofiuorenone, 2-amino-3nitro-7br0mofluorene, 2-amino 3 nitro fl-bromodiphenylenesulfide, 2 amino 3 Intro-7-sulfodiethylaminodiphenylenesulfide, 2-amino 3 nitro-7 bromodi- 1o phenylenesulfone, 2-amino-3-nitro 7-sulfodiethylaminodiphnylenesulfone.; p

As coupling components there may be used the 2-hydroxy-3-naphthoic acid arylamides generally used in the manufacture of ice-colors,

My new dyestuffs are obtainableby diaz'otizing in the usual manner an orthonitramme compound of the kind referredto above and coupling in substance or on the fibre with a 2,3- hydroxynaphthoic acid arylamide. a w I 20 The shades produced on the fibresomewhat depend on the specific components used; as a general rule, however, there may be stated that the azodyestufis produced with an ortho-nitra mino-diphenyleneoxide generallyyield bluish-red to Bordeaux shades, the dyestufis produced with an ortho nitraminocarbazole generally yield violet to corinth shades, the 'dyestuffs' produced with an ortho-nitroamino fluorenone generally yield dull red shades, the dyestufis produced with an ortho-nitraminofiuorene generally yield Bordeaux shades, the dyestuffs produced with orthom'tramino-diphenyleneoxide generally yield Bordeaux shades and the dyestufis produced with an ortho-nitramino-diphenylenesulflde or -sulfcne generally yield red to orange red shades.

The diazotization components usedin-myinvention generally are obtainable by starting with the corresponding amine, diacetylating the amino group, and splitting off the acetyl groups 40 by s nifiwi q Tie invention is I exa 'iiles, without being limited thereto! v Example 1.4 g. of 1-(2',3' -hydroxyna hthoylamino) 2,4-dimthoxy-5-chlorobenhne,- 8 5 cos. or'rurkey red oil a and 8 c'cslo'f caustic soda lye (34 B.) are made into apa'ste [and dissolved to a clearsolutionby-the addition of 200 cos. of hot water, whileboiling'. Aftercooling to a temperature of about 50 C., 4 ccsgof a 50 illustrated bythe rou' win solution of formaldehyde (33%) are added and then the solution is diluted to 1000 cos. with the aid of cold water. In this solution 50 g. of cotton are grounded for hour ata temperature of about 30 C. Then the cotton is squeezed and developed in 1000 cos. of a solution containing 2.3 g. of diazotized o-nitro-2-aminodiphenyleneoxide (prepared according to Borsche, Berichte der Deutschen Chemischen Gesellschaft, vol 56, 1928, page 2504) and 2.8 g. of aluminum sirlfate. After rinsing and soaping, while boiling, Bordeaux shades of good fastness to light and boiling in aqueous caustic soda are obtained. The dyestuff corresponds to the following fonnula:

0 NH OCHz In an analogous manner there is obtained from 2- (2,3'-hydroxynaphthoylamino) -naphthalene a bluish-red of good fastness to light and boiling in aqueous caustic soda.

Compared with the amines not containing the nitro group, the dyestuifs thus obtained exert an improved fastness to light, and further, it is surprising that in spite of the nitro group in o-position to the azo group the fastness to boiling in aqueous caustic soda is not deteriorated.

Example 2.-5 goof 1-(2',3'-hydroxynaphthoylamino)-2-methyl-4-methoxybenzene, 8 cos. of Turkey red oil (50%) and 8 cos. of caustic soda lye (34 B.) are made into a paste and dissolved to a clear solution with 75 cos. of hot water, while boiling. By the addition of 75 cos. of cold water the solution is cooled to a temperature of about 50 0., and 2.5 cos. of a solution of formaldehyde (33%) are added. After 5 minutes the solution is diluted with cold water to 1000 ccs. and 50 g. of cotton are grounded in the usual manner. Then the cotton is squeezed and developed in a solution containing 2.3 g. of diazotized 2-nitro-3-aminocarbazole (prepared according to Kehrmann and'Zweifel, Helvetia Chimica Acta, Vol XI, p. 1213 seq.) and 2.8 g. of aluminum sulfate. After acidifying, rinsing and soaping, a corinth is obtained which exerts good fastness to light and boiling in aqueous caustic soda. The dyestuff corresponds to the followingformulaz I oo .6 I i DIE-Q0011;

In an analogous manner there is obtained from 1- (2',3'-hydroxynaphthoylamino) 2 -methyl- 4 chlorobenzene a corinth of good fastness to light and boiling in aqueous caustic soda, and from 2- (233'-hydroxynaphthoylamino) -naphtha1ene a bluish-violet exerting good fastness to light and boiling in aqueous caustic soda.

Compared with the amines not containing the nitro group, the dyestuffs thus obtained exert an improved fastness to light, and further, it is surprising that in spite of the nitro group in 0- position to the azo group the fastness to boiling in aqueous caustic soda is not deteriorated.

In an analogous manner there is obtained: from 2-amino-3-nitrofiuorenone and 1-(2,3'-hydroxynaphthoylamino) 4 methoxybenzene a brownish-red .dyestuif of the following formula:

WIND, N: C()

from 2-amino-3-nitrofluorenone and 1-(2,3'-hydroxynaphthoylamino) -3-nitrobenzene a brown- 7 ish-red dyestuff of the following formula:

from 2-amino-3-nitrofluorene and 1-(2',3-hydroxynaphthoylamino) -3-chloro-4,6-dimethoxybenzene a reddish-Bordeaux .dyestuif of the following formula:

CHI 01 l O NH OCH:

from 2-amino-3-nitrodiphenylenesulfide and 1- (2',3'-hydroxynaphthoylamino) 2 methyl-4- chlorobenzene .a Bordeaux-red dyestufi of the following formula:

from 2-amino-3-nitrodiphenylenesu1fide and 2- (2' ,3 hydroxynaphthoylamino) naphthalene a Bordeaux-red dyestuff of the following formula:

I wfiol N: V v r Ed 0 r g and from 2-amino-3-nitrodiphenylenesulfone and 1-(2',3-hydroxynaphthoylamino) -2-methyl 4- chloro-benzene a reddish-orange dyestufl of the following formula:

wlqol 8 in which R is a diphenylene radical, R is a radical of the aromatic series and the -NO2 group stands in 0-position to the azo group, said dyes yielding when produced on the fiber, generally corinth to orange-red shades of good fastness to light and to boiling in aqueous caustic soda.

2. The azodyestufis of the general formula:

wherein X stands for a divalent radical of the group consisting of NH, the hydrogen atom of which may be substituted by a hydrocarbon radical, S, S0, S02, 0, CH2 and CO, wherein R stands for a radical of the aromatic series, the N02- group stands in o-position to the azo group, and wherein the nuclei may be further substituted by substituents selected from the group consisting of alkyl, alkoxy, aryloxy, aralkyloxy, halogen, the nitro group acylamino, a sulfoneamide group one or both hydrogen atoms of which are substituted by hydrocarbon radicals, sulfonealkyl, sulfonearalkyl, sulfonearyl, an alkyl ketone or aryl ketone, yielding, when produced on the fibre, generally corinth to orange-red shades of good fastness to light and boiling in aqueous caustic soda.

3. The azodyestuff of the following formula:

HA) CO CHI yielding, when produced on the fibre, a Bordeaux 2 of excellent fastness to light and boiling in aqueous caustic soda.

4. The azodyestufi of the following N02 EH5 I O f NH- OCH: H

yielding, when produced on the fibre, a corinth of excellent fastness to light and boiling in aqueous caustic soda.

5. Fibre dyed with the dyestuffs as claimed in claim 2.

6. Fibre dyed with the dyestuff as claimed in claim 3.

7. Fibre dyed with the dyestufi as claimed in claim 4.

formula:

FRIEDRICH MUTH. 

